Wastewater by Plain and

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Ind. Eng. Chem. Res. 2009, 48, 3619–3627

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GENERAL RESEARCH Treatment of Cyanide Bearing Water/Wastewater by Plain and Biological Activated Carbon Rajesh Roshan Dash,*,† Chandrajit Balomajumder,*,‡ and Arvind Kumar*,§ Department of CiVil Engineering, NIT Hamirpur, Hamirpur-177005, HP, India, and Department of Chemical Engineering, and Department of CiVil Engineering, IIT Roorkee, Roorkee-247667, Uttarakhand, India

Comparative study of biodegradation and adsorption alone with simultaneous adsorption and biodegradation (SAB) process was carried out along with a brief review of the processes. Adsorption and SAB studies were carried out in plain and Pseudomonas putida immobilized granular activated carbon (GAC), whereas biodegradation was conducted with suspended cultures of P. putida. P. putida used iron cyanide as the sole source of nitrogen at an initial pH of 7.0 and temperature of 30 °C. At an initial iron(II) cyanide concentration of 100 mg/L, removal efficiencies of cyanide by adsorption, biodegradation, and SAB were found to be 81.5%, 78.2%, and 96.7%, respectively. The initial ferrocyanide concentrations of 50-350 mg CN-/L were taken for the study. The microbes adopted to grow at maximum cyanide concentration were harvested, and their ability to degrade cyanide were measured in both biodegradation and SAB. The removal efficiency of biologically activated granular activated carbon (BAC) was found better as compared to that of plain GAC. It was also found that the SAB process is more effective than adsorption and biodegradation alone. 1. Introduction Cyanide is highly toxic to humans and aquatic organisms.1 It is a potent inhibitor of respiration due to its extreme toxicity toward cytochrome oxidase and by tightly binding to terminal oxidase.2 The presence of cyanide in effluents can attain considerable concentrations and occurs both naturally (biogenes by plants and microorganisms) and from human activities (wastes from metal plating, ore leaching, production of synthetic fibers, plastics, pharmaceuticals, coal gasification, metal extraction, and cyanogenic crop plants), which forms the major source of contamination of natural water by this compound.3 Cyanide’s strong affinity to metal ions makes it a favorable agent in electroplating/metal plating and extraction of gold and silver in mining industries, and hence is produced in a large volume from these industries.4 Cyanide compounds are present in environmental matrices and waste streams as simple and complex cyanides, cyanates, and nitriles.5,6 In the presence of metal ions, such as nickel, copper, zinc, and iron, etc., cyanide forms complex compounds of varying toxicity and stability.1,7,8 Although metal-cyanide complexes by themselves are much less toxic than free cyanide, their dissociation releases free cyanide as well as the metal cation, which can also be toxic.7 Ferrocyanides, which are the well-known hexacyano complexes of iron, are also very recalcitrant cyano-metal complexes.1 However, both ferro- and ferricyanides decompose to release free cyanide when exposed to direct ultraviolet light in aqueous solutions.7 * To whom correspondence should be addressed. Tel.: +91 1972 254348. Fax: +91 1972 223834. E-mail: [email protected], [email protected] (R.R.D.). Tel.: +91 1332 285321. Fax: +91 1332 276535/273560. E-mail: [email protected], [email protected] (C.B.). Tel: +91 1332 285431. Fax: +91 1332 273560. E-mail: [email protected] (A.K.). † Department of Civil Engineering, NIT Hamirpur. ‡ Department of Chemical Engineering, IIT Roorkee. § Department of Civil Engineering, IIT Roorkee.

To protect the environment and water bodies, wastewater containing cyanide must be treated before discharging into the environment.9 The acceptable level of cyanide at the effluent outlet lies between 4 and 40 µM.3 The U.S. health service, Central Pollution control Board, India, and many other countries cite 0.2 mg/L as the permissible limit for cyanide in effluent.1,7 Hence, the removal of cyanide from industrial wastewater is required before it is discharged into municipal sewers.10 The common methods used to reduce the cyanide level below 0.2 mg/L for disposal of the effluent are based on cyanide recovery by acidification and/or destruction by chemical oxidation.11,12 Alkaline chlorination, ozonization, and wet-air oxidation are chemical oxidation methods, commonly used for treatment of cyanide contained wastewater.13,14 However, these methods are expensive and hazardous chemicals are used as the reagents (chlorine and sodium hypochlorite),14 and this treatment produces toxic residues, which implies the presence of an additional level of detoxification.3,9 The other treatment methods used such as Caro’s acid, copper-catalyzed hydrogen peroxide, electrolytic oxidation, ion exchange, acidification, AVR (acidification, volatilization, and reneutralization) process, lime-sulfur, reverse osmosis, thermal hydrolysis, and INCO process (by SO2/air)4,7,8 are highly expensive and cannot completely degrade all cyanide complexes in many cases.9 Despite the toxicity of cyanide to living microorganisms, biological treatments are feasible and well-proven alternatives to other methods for cyanide destruction, because a wide range of microorganisms are known to metabolize such chemicals.1 Biological treatment is a costeffective and environmentally acceptable method for cyanide removal as compared to the other techniques currently in use.9,15,16 The physical process of granular activated carbon (GAC) adsorption is also widely used in full-scale applications as a polishing process for the removal and recovery of low levels of cyanide contained in process solutions.17,18 1.1. Background of the Processes. Hundreds of plant and microbial species (bacteria, fungi, and algae) can detoxify

10.1021/ie071299y CCC: $40.75  2009 American Chemical Society Published on Web 02/20/2009

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cyanide quickly to environmentally acceptable levels and into less harmful byproduct. The cyanide molecule includes both carbon and nitrogen atoms, and in the presence of microorganisms and oxygen it will undergo degradation through an aerobic biological process.17 Cyanide also degrades biologically through anaerobic processes although much more slowly.17 Cyanogenic and noncyanogenic microorganisms are found to have specific enzymes and pathways for the cyanide degradation.6 Most reports demonstrated the ability of microorganisms to utilize cyanide as a source of nitrogen or both carbon and nitrogen. Metabolism of cyanide by various strains of Pseudomonas, Acinetobacter, Bacillus, and Alcaligenes have been reported.19-22 Degradation of cyanide compounds by fungi such as Fusarium solani, Fusarium oxysporum, Gloeocercospora sorghi, Fusarium lateritum, and Stemphylium loti23-28 have also been reported. Babu et al. (1996) utilized cell free extracts of P. putida for conversion of cyanide complexes to ammonia.29 Kunz et al. (1994) reported that NCIMB strain of Pseudomonas fluorescens degraded cyanide via the activities of several cyanide-degrading enzymes such as oxygenase, cyanide nitrilase, and cyanide hydratase.30 A Pseudomonas species degraded cyanide through a pathway where cyanide is converted to ammonium and formate under both aerobic and anaerobic conditions.14 A Burkholderia cepacia strain C-3 was found to utilize cyanide as a nitrogen source in liquid minimal medium at pH 10. However, in the presence of heavy metals such as Cu2+, Fe3+, Ni2+, Co2+, Mn2+, and Mo2+ and phenol, the growth of B. cepcia was inhibited in minimal medium.31 Several other investigations of the microbial destruction of cyanide have been reported including laboratory, pilot, and fullscale facilities. Attached growth processes and combined processes such as oxic/anoxic processes have been proved to be advantageous for the cyanide detoxification.7 Biodegradation of cyanide compounds by immobilized cells of Pseudomonas species, Klebsiella oxytoca, and F. oxysporum on various packing materials such as agar, alginate cellulose, and carrageenan have been found to be more effective as compared to suspended cultures.3,32-34 However, these studies mainly focus on biodegradation of cyanide compounds. Although biological treatment process is cost-effective and environmental friendly, it cannot treat a high concentrated waste or waste with heavy load. Apart from degradation, biosorption processes also exist, in which microorganisms adsorb the toxic compounds instead of degrading it. Several fungal species are there (Aspergillus fumigatus, Aspergillus niger, Aureobasidium pullulans, Cladosporium cladosporioides, Fusarium moniliforme, Fusarium oxysporum, Mucor hiemalis), which can act as biosorbents for cyanide compounds.35 Aksu and Gu¨len (2002) reported binary biosorption of iron(II) and iron(III) cyanide complex ions on Rhizopus arrhizus.36 Biosorption of metal cations has been studied extensively by several researchers, and the process has been reported to be developed for a practical scale in recent times.37 There are also reports on the treatment of low concentration of cyanide by adsorption.38-40 Activated carbon adsorption is known to be usually unaffected in its treatment efficiency by temporal qualitative and quantitative changes of pollutants contained in wastewater. Especially, granular activated carbon with a narrow size range was reported to have high treatment efficiency even for wastewater containing a high pollutant concentration.41 Usually, the substances, which are easily adsorbed, are also hardly biodegradable; frequently the opposite is also valid.42 Therefore, the adsorption and the biodegradation successfully

supplement each other in the various schemes of wastewater treatment. Biologically treated wastewater can, for instance, be finally cleared with the help of a carbon filter. Inversely, the activated carbon adsorption can possibly allow the removal of toxic contaminants from wastewater and thus ensure a stable biological post treatment of wastewater.43 In biologically activated carbon (BAC) theories, the most widely accepted meaning of bioregeneration is that some adsorbate, which has been adsorbed on the carbon, can be degraded by microorganisms with the carbon bed in normal operation. Because the size of bacterial cells is too large for infiltration into carbon pores, the biodegradation in pores takes place by means of exocellular enzymes, which are capable of diving into micropores and can interact with adsorbed substrate and promote its hydrolytic decay.43 However, few attempts have been made for the combined process for adsorption and biodegradation of metal cyanides on biologically active adsorbents. 1.2. Present Study. In the present study, adsorption and biodegradation techniques were used individually and combined for removal of cyanide from iron cyanide bearing aqueous solutions. Adsorption and SAB (simultaneous adsorption and biodegradation) of iron cyanide bearing synthetic solutions were performed separately in batch reactors with plain and Pseudomonas putida (MTCC Code 1194) immobilized granular activated carbon (GAC), respectively. Biodegradation study with P. putida was also carried out in batch reactors. The optimization of environmental conditions and process parameters for all three processes was carried out. Percentages of removal of cyanide by the three processes, that is, adsorption, biodegradation, and SAB, were compared. 2. Experimental Program 2.1. Properties of Cyanide Solutions and Adsorbent. All of the chemicals were of analytical grade, and solutions were prepared by Milli-Q water (Q-H2O, Millipore Corp. with resistivity of 18.2 MΩ cm). The stock ferrocyanide solution of 1 mg CN-/mL was prepared by dissolving 2.7 g of K4Fe(CN)6 · 3H2O in 1 L of Milli-Q water. Study on removal of cyanide by adsorption, biodegradation, and SAB processes was conducted at initial ferrocyanide concentrations (Ci) of 50, 100, 200, 300, and 350 mg CN-/L. The cyanide concentrations taken for the present studies were in accordance with the concentration of cyanide in actual wastewaters produced from various industries.44 The GAC particles having apparent density 400 g/L, particle size 2-5 mm, BET surface area 583.35 m2/g, and micropore ( 0.9 for all cases) allowed computation of metal cyanide adsorption capacities. The experimental data obtained in the study were found to obey basic principles underlying the models, that is, monolayer adsorption and heterogeneous surface adsorption at constant adsorption energy.35 From Table 1 it was evident that the R value lies within 0-1 for all cases and the n value is also greater than 1 and lies within 1-5. Therefore, both Langmuir and Freundlich isotherms can explain the adsorption as well as SAB processes.54 It was also observed that for both plain and BAC the Qm values in Langmuir isotherms were greater than the corresponding Kf

values in Freundlich isotherms. This indicated that the Langmuir isotherm was a better fit for the description of the adsorption process than was the Freundlich isotherm.42,43 This indicated that monolayer adsorption predominated. Qm and K1 values of BAC were more than those of plain GAC in Langmuir isotherms. This indicates more adsorption capacity of the adsorbents and more energy of adsorption in SAB process. This may be due to the dominating role of BAC over plain GAC. 4. Conclusion In the present study, the capability of P. putida to remove ferrocyanide complex individually and simultaneously by adsorption and biodegradation from aqueous solution was examined. Overall, the results presented and discussed herein added significance to the knowledge to adsorption, biodegradation, and SAB, including the evaluation of feasibility of the SAB process for removal of cyanide compounds. Better removal efficiency was found for ferrous cyanide complex with higher concentrations by the combined process of adsorption and biodegradation. Biodegradation of ferrocyanide was not possible at higher concentrations, but in the presence of BAC, there was the possibility of biological growth and degradation in high concentrated cyanide bearing aqueous solutions. The combined process was more effective and less time-consuming. It was observed from the biodegradation process that biodegradation delayed due to the increase in lag phase of P. putida at higher concentration of cyanide. In the case of the SAB process, due to adsorption a certain amount of cyanide ions was removed, and then the biodegradation process was started along with the adsorption. The toxicity of the cyanide in the solution was reduced due to adsorption on monolayer, and cyanide was easily available for degradation. The cyanide adsorbed on the biologically active GAC surface could be easily biodegraded by microbes as GAC acts as an enrichment surface and attached growth gave better efficiency. This made the combined process more effective than the single process and gave better efficiency. The SAB process can be used successfully for removal of various cyanide compounds from cyanide bearing industrial wastewaters. The study, therefore, is a pointer toward alternative possibilities of toxicity removal through SAB and its respective merits. Acknowledgment We would like to thank All India Council of Technical Education (AICTE), India, for funding for this research work in the form of a National Doctoral Fellowship. We are thankful to the Department of Civil Engineering, Department of Chemical Engineering, and Institute Instrumentation Center of Indian Institute of Technology Roorkee, India, for providing facilities to carry out this research work. We are also grateful to the esteemed reviewers for their valuable comments and suggestions, and for reviewing this paper. Note Added after ASAP Publication: This article was released ASAP on February 20, 2009 with a minor error in equation 1. The correct version was posted on February 25, 2009.

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Supporting Information Available: Sterility, revival of freeze-dried MTCC cultures, determination of optical density, dry cell weight and cell concentration in solution, and acclimatization/adaptation of cultures to cyanide. This material is available free of charge via the Internet at http://pubs.acs.org. Nomenclature (adsorption)E ) adsorption experimental data (adsorption)F ) adsorption predicted data from Freundlich isotherm (adsorption)L ) adsorption predicted data from Langmuir isotherm (SAB)E ) SAB experimental data (SAB)F ) SAB predicted data from Freundlich isotherm (SAB)L ) SAB predicted data from Langmuir isotherm Ce ) equilibrium concentration of adsorbate in aqueous solution (mg/L) Ci ) initial ferrocyanide concentration (mg CN-/L) Dc ) dose/mass of GAC in aqueous solution (g/L) Kf ) Freundlich constant (mg/g)/(mg/L)1/n Kl ) Langmuir constant related to enthalpy (energy/intensity) of adsorption M ) weight of GAC taken n ) Freundlich constant Pc ) particle size of GAC (mm) Qe ) mass of pollutant adsorbed on unit mass of GAC at equilibrium (mg/g) Qm ) Langmuir constants related to adsorption capacity (mg/g) Sa ) agitation speed (rpm) ta ) agitation time (h) X ) amount of cyanide adsorbed

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ReceiVed for reView September 27, 2007 ReVised manuscript receiVed December 12, 2008 Accepted January 26, 2009 IE071299Y